JP2007269356A - Leakage detecting sheet and container carrying leakage detecting sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a leakage detecting sheet capable of a detecting the leakage of a liquid content by viewing appearance when the leakage of the liquid content is generated from the micro-cracking of a bottle filled with a liquid medicine or the like to include it, and a container carrying the leakage detecting sheet. <P>SOLUTION: The leakage detecting sheet 10 is carried by the outer face of a container 5 for filling an amino compound-containing liquid and detects the leakage of the amino compound-containing liquid caused by the breakage of the container. A color developing agent-incorporated pressure-sensitive adhesive layer 2 containing a ninhydrin compound (a) expressed by a general formula (I) (wherein R is a hydrogen atom or an alkyl group) and substantially containing no nitrogen-containing compound (b) is carried on one surface of a transparent substrate sheet 1. The container carries the leakage detecting sheet 10 on its outside surface. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a leak detection sheet and a container carrying the leak detection sheet. According to the leakage detection sheet of the present invention, for example, even when a minute crack occurs in a container filled with a liquid medicine, the occurrence of the crack can be detected effectively.

  In recent years, liquid investigational drugs have been transported in the form of frozen products (for example, in the form of frozen ampoules and vials) without lyophilization for the purpose of simplifying the manufacturing process and introducing them to the market early. Increasingly, thawing and ingesting. However, the preparations of the frozen ampule bottles and vial bottles are problematic because the bottles may break during the distribution process. If the bottle is severely damaged, the liquid content will leak when thawed.For example, the display label may get wet due to cracking of the ampule bottle or vial, or leakage of the contents. Can be easily removed as. However, if only minute cracks occur, even if the liquid content is leaked when thawing, there is no visible change in the appearance of the bottle or the display label, and it may not be confirmed. . In this way, defective products that cannot be distinguished from non-defective products are delivered to the actual medical site and administered to humans as they are. May be incurred. However, no technology has been proposed in the past that enables easy discrimination by visual inspection even when liquid content leaks from minute cracks. Therefore, it has been desired to develop a display label that can detect the leakage of the liquid contents due to such minute cracks by visual inspection.

  Conventional labeling labels used on ampoule bottles and vials are not only sticky to the outer surface of the bottle, but also function as a display that correctly specifies the product name, usage, and dosage, and are based on cushioning. Although the function of preventing broken bottles using materials has been studied, the function of detecting leakage of liquid contents has not been taken up as a problem.

As will be described later, the present invention uses a ninhydrin color reaction to realize leakage detection of a liquid content, but such a technique has not been known at all. Incidentally, as a detection technique using a ninhydrin color reaction, for example, a detection method for small animals (for example, mites) is known (Patent Document 1). However, in this detection method, the adhesive surface is pressed against a carpet or the like to capture a small animal (for example, ticks), the captured small animal (for example, ticks) is crushed to extrude body fluid, and the body fluid reacts with ninhydrin. This is a technology that is unrelated to display labels such as bottles.
A fingerprint detection sheet using a ninhydrin color reaction is also known (Patent Document 2). However, this fingerprint detection sheet presses the pressure-sensitive adhesive layer against the fingerprint attachment site on the specimen surface, and transfers the residue forming the fingerprint ridge line from the specimen surface to the pressure-sensitive adhesive layer, thereby forming the fingerprint ridge line. It reacts with the protein, peptide, amino acid, etc. contained in the residue to react with the ninhydrin compound contained in the adhesive layer to develop color, and is a technology unrelated to the label on the bottle. is there.

Japanese Patent Laid-Open No. 62-296828 JP 2000-186269 A

  Therefore, the present invention solves the above-mentioned problems that have not been taken up conventionally, that is, microcracks are generated in bottles (for example, ampoule bottles and vial bottles) filled with liquid medicine. An object of the present invention is to provide a leakage detection sheet that can be easily detected by visual inspection even when a liquid content leakage that is normally impossible or difficult to visually confirm occurs.

（式中、Ｒは水素原子又はアルキル基である）
で表されるニンヒドリン化合物を含有し、窒素含有化合物を実質的に含まない発色層を担持することを特徴とする、前記漏出検知用シートによって解消することができる。 According to the present invention, there is provided a sheet for detecting leakage of the amino compound-containing liquid due to breakage of the container, provided on the outer surface of the container for filling an amino compound-containing liquid according to the present invention. On one surface, the general formula (I):

(Wherein R is a hydrogen atom or an alkyl group)
It can be solved by the leakage detection sheet, characterized in that it carries a color-developing layer containing a ninhydrin compound represented by the formula (1) and substantially free of a nitrogen-containing compound.

  In a preferred embodiment of the detection sheet according to the present invention, the transparent substrate sheet is a transparent non-shrinkable substrate sheet or a transparent heat-shrinkable substrate sheet.

In a preferred embodiment of the detection sheet of the present invention in which the transparent substrate sheet is a transparent non-shrinkable substrate sheet, the color developing layer is a color developing pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition.
In this aspect, the color-forming pressure-sensitive adhesive layer can have a single-layer structure of a color-forming agent-mixed pressure-sensitive adhesive layer containing the ninhydrin compound in the pressure-sensitive adhesive composition. The layer can contain a colorant.
Further, in this embodiment, the color-forming pressure-sensitive adhesive layer is provided on one surface of the transparent base sheet, and does not contain a pressure-sensitive adhesive composition, but contains the ninhydrin compound and the color-forming agent-containing layer. It can consist of a two-layer structure with the adhesive layer provided on the layer, and in this embodiment, the color former-containing layer and / or the adhesive layer can further contain a colorant.

In a preferred embodiment of the detection sheet of the present invention in which the transparent base sheet is a transparent heat-shrinkable base sheet, the color developing layer is a color former-containing layer that does not contain an adhesive composition.
In this embodiment, the color former-containing layer can be a single-layer color former-containing layer having a single-layer structure containing the ninhydrin compound, and the single-layer color former-containing layer further contains a colorant. be able to.
Further, in this aspect, the color former-containing layer can be a color former-containing layer having a multilayer structure of the single-layer color former-containing layer and one or more auxiliary layers not containing the color former. In the aspect, the monolayer color former-containing layer and / or the auxiliary layer may further contain a colorant.

The present invention also relates to a container that carries the leakage detection sheet on the outer surface in a state where the coloring layer is in contact with the outer surface of the container.
In a preferred embodiment of the container according to the present invention, the leakage detection sheet is attached and supported on the outer surface in a state where the coloring adhesive layer is in contact with the outer surface of the container.
In another preferred embodiment of the container according to the present invention, the leakage detection sheet is thermally contracted, and the color former-containing layer is carried on the outer surface in contact with the outer surface of the container.

  According to the leakage detection sheet of the present invention, a microcrack is generated in a bottle (for example, an ampoule bottle or a vial bottle) filled with a liquid medicine or the like, and usually cannot be visually confirmed. Even when a liquid content leakage of a degree occurs, the leakage can be easily detected by visual inspection.

The leakage detection sheet of the present invention carries a color developing layer on one surface of the transparent substrate sheet. The coloring layer contains a ninhydrin compound represented by the general formula (I) as a coloring agent. The ninhydrin compound used as the color former in the present invention is a ninhydrin corresponding to the case where R is a hydrogen atom in the general formula (I), or the case where R is an alkyl group in the general formula (I). O-alkylated ninhydrin. The alkyl group is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Group, heptyl group, octyl group, nonyl group, decyl group, 3-methyl-1-butyl group, 2-methyl-1-pentyl group, 2,2-diethylethyl group, 3,5,5-trimethyl-1- A hexyl group, a 2-ethylhexyl group, etc. can be mentioned. The alkyl group is more preferably a linear or branched alkyl group having 4 to 8 carbon atoms from the viewpoint of further improving the organic solvent solubility of the O-alkylated ninhydrin.
Said O-alkylated ninhydrin comprises ninhydrin and the formula:
R ¹ —OH
(Wherein R ¹ is an alkyl group)
It can manufacture easily by making the compound represented by these react.

In the leakage detection sheet of the present invention, as the transparent substrate sheet, for example, a transparent non-shrinkable substrate sheet or a transparent heat-shrinkable substrate sheet can be used. When the transparent substrate sheet is a transparent non-shrinkable substrate sheet, the color developing layer provided on one surface thereof is a color developing pressure-sensitive adhesive layer, and the leakage detection sheet of the present invention having this structure, It will be called "adhesive label type sheet" or simply "adhesive label". Further, when the transparent substrate sheet is a transparent heat-shrinkable substrate sheet, the coloring layer provided on one surface thereof is a coloring agent-containing layer, and the leakage detection sheet of the present invention having this structure Is referred to as a “heat-shrinkable sheet”.
Hereinafter, the “adhesive label type sheet” (or “adhesive label”) will be described first, and then the “heat-shrinkable sheet” will be described.

  The pressure-sensitive adhesive label type sheet according to the present invention carries a color-forming pressure-sensitive adhesive layer on one surface of a transparent non-shrinkable base sheet. The color-forming pressure-sensitive adhesive layer may have a single-layer structure or a structure having two or more layers. The pressure-sensitive adhesive label sheet of the present invention in which the color-forming pressure-sensitive adhesive layer has a single-layer structure is hereinafter referred to as a mixed-type pressure-sensitive adhesive label, and the pressure-sensitive adhesive label-type sheet of the present invention in which the color-forming pressure-sensitive adhesive layer has a structure of two or more layers. Hereinafter, it may be referred to as a separation type adhesive label.

  FIG. 1 shows a state in which a mixed adhesive label 10 according to the present invention is attached to the surface of a bottle 5. The mixed adhesive label 10 includes a transparent non-shrinkable base sheet 1 and a color former mixed adhesive layer 2, and is attached to the surface of the bottle 5 by the color former mixed adhesive layer 2. FIG. 2 shows a state where the separation-type adhesive label 10A according to the present invention is attached to the surface of the bottle 5. The separation-type adhesive label 10A is provided on the transparent non-shrinkable base sheet 1, the color former-containing layer 3 provided on one surface of the transparent non-shrink base sheet 1, and the color former-containing layer 3 The pressure-sensitive adhesive layer 4 does not contain the color former and is adhered to the surface of the bottle 5 by the pressure-sensitive adhesive layer 4. In addition, since each sectional view attached to this specification is mainly intended to explain the layered structure of the adhesive label, the thickness of each layer is exaggerated and the relative ratio of the thickness of each layer is also accurate. It is not a thing.

  In the color former-mixed pressure-sensitive adhesive layer of the mixed-type pressure-sensitive adhesive label according to the present invention, the content of the ninhydrin compound represented by the general formula (I) is not particularly limited. Preferably it is 0.5 weight part-50 weight part with respect to 100 weight part of adhesive polymer solid content contained in the adhesive composition (after-mentioned) used for formation, More preferably, it is 1.0 weight part-30 weight part. Contained in an amount. When the content is less than 0.5 parts by weight, the color of the leaked liquid content may become thin, and when it exceeds 50 parts by weight, the ninhydrin compound is uniformly dissolved in the pressure-sensitive adhesive composition. May be difficult, or the adhesive properties may be impaired. In the range of 2.5 parts by weight to 20 parts by weight, a clear color is obtained and the adhesive physical properties are also good, which is particularly preferable.

  In the color former-containing layer of the separation type pressure-sensitive adhesive label according to the present invention, the content of the ninhydrin compound represented by the general formula (I) is not particularly limited, but the coating used for forming the color former-containing layer is not limited. The composition is contained in an amount of 0.5 to 50 parts by weight, more preferably 1.0 to 30 parts by weight in 100 parts by weight (solid content) of the composition for use (described later). If the content is less than 0.5 parts by weight, the color of the leaked liquid content may be thin, and if it exceeds 50 parts by weight, the ninhydrin compound is uniformly dissolved in the coating composition. May be difficult, and application suitability may be impaired. In the range of 2.5 parts by weight to 20 parts by weight, it is particularly preferable because a clear color is obtained and the coating suitability is also good.

  The pressure-sensitive adhesive composition used for forming the color-agent-containing pressure-sensitive adhesive layer of the mixed-type pressure-sensitive adhesive label of the present invention, and the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer containing no color-forming agent of the separation-type pressure-sensitive adhesive label (hereinafter collectively) All of the pressure-sensitive adhesive compositions are substantially free of nitrogen-containing compounds. Here, “substantially free” means coloring by causing a ninhydrin reaction with the ninhydrin compound represented by the general formula (I) in the pressure-sensitive adhesive composition of the color former-mixed pressure-sensitive adhesive layer. In the pressure-sensitive adhesive layer not containing a color former, it means that it contains no nitrogen-containing compound in an amount greater than or equal to the amount of ninhydrin represented by the general formula (I) contained in the adjacent color former-containing layer. It means that a nitrogen-containing compound is not contained in an amount greater than the amount that causes a ninhydrin reaction with the compound to cause coloration.

  A normal pressure-sensitive adhesive composition may contain a nitrogen-containing compound, but if it is contained in the pressure-sensitive adhesive composition used in the present invention, the nitrogen-containing compound may cause a ninhydrin reaction and become colored. Is, for example, ammonia, various ammonium salts, various amine compounds, various amide compounds, various aziridine compounds, various isocyanate compounds, various urethane compounds, various imine compounds, various imide compounds, and / or various urea derivatives, The compound which may be converted into ammonia and an amino group containing compound can be mentioned. Such a nitrogen-containing compound cannot be contained in the pressure-sensitive adhesive composition used in the present invention.

  The pressure-sensitive adhesive composition used in the present invention contains a pressure-sensitive polymer. As the adhesive polymer, an acrylic polymer or a rubber polymer can be used as long as it does not substantially contain a nitrogen-containing compound. However, the acrylic polymer is excellent in transparency and weather resistance. Is preferred.

  The adhesive polymer can be prepared by polymerizing (or copolymerizing) a hydrophilic monomer and a hydrophobic monomer at an arbitrary quantitative ratio. When using an adhesive polymer consisting only of hydrophilic monomers, penetration of the leaked liquid into the adhesive layer is improved, and the time for diffusion can be accelerated, so detection can be done quickly, but because it diffuses over a wide area, Initial color development may decrease with time. On the other hand, if an adhesive polymer consisting only of a hydrophobic monomer is used, the penetration of the leaked liquid into the adhesive layer will be reduced and the diffusion time will be delayed, so detection will be delayed, but diffusion of the colored dye will also be suppressed. Therefore, high color developability can be obtained. In order to effectively detect leakage of a liquid containing 0.001 to 10% by weight of an amino compound, an adhesive polymer obtained by copolymerizing the ratio of the hydrophilic monomer in the total monomer to 3 to 100% by weight Is preferably used.

  Examples of the adhesive polymer used in the present invention include an acrylic polymer selected from a homopolymer and a copolymer having a (meth) acrylic acid ester monomer as a main structural unit, a (meth) acrylic acid ester monomer, and Examples thereof include a copolymer with a functional group-containing monomer (described later) other than the (meth) acrylic acid ester monomer, or a mixture of these (co) polymers.

  Examples of the hydrophobic monomer in the (meth) acrylic acid ester monomer include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth) acrylate and ethyl. (Meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc. can be mentioned.

〔式中、Ｒ^１１は水素原子又はメチル基であり、Ｒ^１２は水素原子又は炭素数１〜８のアルキル基であり、ｎは１以上（好ましくは１〜３）の整数である〕
で表されるポリアルキレングリコール骨格を有するエーテル結合含有（メタ）アクリル酸エステル類が挙げられ、例えば、エチレングリコールモノ（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、トリエチレングリコールモノ（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、２−（２−メトキシエトキシ）エチル（メタ）アクリレート、２−（２−エトキシエトキシ）エチル（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、エトキシトリエチレングリコール（メタ）アクリレートなどを挙げることができる。 The hydrophilic monomer in the (meth) acrylate monomer is represented by the general formula (II):

[Wherein, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 or more (preferably 1 to 3)]
Ether bond-containing (meth) acrylic acid esters having a polyalkylene glycol skeleton represented by, for example, ethylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, methoxytriethylene glycol (Meth) acrylate, ethoxytriethylene glycol (meth) acrylate, etc. can be mentioned.

  The functional group-containing monomer [functional group-containing monomer other than (meth) acrylic acid ester monomer] is a carboxyl group that does not cause a color reaction with the ninhydrin compound as a functional group, a carboxylate group, a hydroxyl group, an epoxy group, It is a monomer having a sulfonic acid group and / or a sulfonic acid group and copolymerizable with the (meth) acrylic acid ester monomer. Among them, examples of the hydrophilic monomer include acrylic acid, methacrylic acid, sodium acrylate, 2-hydroxyethyl (meth) acrylate, vinyl sulfonic acid, or potassium 3-acryloyloxypropane-1-sulfonate, and the like. Examples of the ionic monomer include glycidyl (meth) acrylate.

  Moreover, when synthesizing the adhesive polymer, it is necessary to take care that the adhesive composition itself does not cause a ninhydrin reaction. In order to synthesize an adhesive polymer, addition polymerization such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization is preferably used. Among them, radical solution polymerization is simple and preferably used. In carrying out these polymerizations, a compound such as a polymerization initiator and a polymerization solvent is simultaneously used in addition to the above-mentioned pressure-sensitive monomer, so that these compounds also remain or exist in the pressure-sensitive adhesive composition. Therefore, it is necessary to use a compound that does not cause a ninhydrin reaction when carrying out the polymerization. Specifically, it is necessary to use a polymerization initiator or a polymerization solvent that does not have a functional group of a nitrogen compound that may cause coloration by causing the ninhydrin reaction, and examples of the polymerization initiator include potassium persulfate and Persulfate polymerization initiators such as sodium persulfate (not including ammonium persulfate), azo polymerization initiators such as 2,2′-azobisisobutyronitrile and 4,4 ′-(4-cyanovaleric acid) Alternatively, an organic peroxide polymerization initiator such as benzoyl peroxide or tert-butyl peroxyisobutyrate can be used. The content of the polymerization initiator can be arbitrarily adjusted in order to adjust the viscosity of the pressure-sensitive adhesive composition and the molecular weight of the pressure-sensitive adhesive polymer. Generally, the content of the polymerization initiator is 100 parts by weight of the pressure-sensitive adhesive monomer used. The amount is 0.01 part by weight to 0.5 part by weight.

  In the pressure-sensitive adhesive composition used in the present invention, the solid content of the pressure-sensitive adhesive polymer is not particularly limited, but in 100 parts by weight of the pressure-sensitive adhesive composition used in the present invention, preferably 5 parts by weight to It is contained in an amount of 90 parts by weight, more preferably 10 parts by weight to 70 parts by weight. If the content is less than 5 parts by weight, the physical properties of the adhesive may be impaired, and if it exceeds 90 parts by weight, the applicability of the adhesive composition may be hindered. The range of 10 parts by weight to 70 parts by weight is particularly preferable because the applicability of the adhesive composition and the adhesive properties of the adhesive composition layer are good.

  In order to impart heat resistance, durability and processability to the pressure-sensitive adhesive composition used in the present invention, and to control the physical properties of the pressure-sensitive adhesive, the functional group of the pressure-sensitive adhesive polymer is used to react with these. A functional compound can be mix | blended suitably. Examples of the polyfunctional compound used for this purpose include an epoxy compound, a metal chelate compound, a metal salt, and / or a reactive phenol resin. Among these compounds, a compound that does not cause a ninhydrin reaction. Depending on the type of the functional group of the adhesive polymer, one or two or more types can be appropriately selected and used. Although content of the said polyfunctional compound is not specifically limited, Generally 0.01 weight part-25 with respect to 100 weight part of said adhesive polymer solid content contained in the adhesive composition used by this invention. It is the amount by weight.

The solvent-based composition used in the present invention can be an aqueous system, a water / organic solvent mixed system composition, or an organic solvent-based composition.
The aqueous or water / organic solvent mixed composition is water as a solvent, or water and a polar organic solvent, for example, alcohols (for example, methanol, ethanol, or isopropanol), esters (for example, ethyl acetate), And / or a mixture with ketones (for example, acetone, methyl ethyl ketone, etc.) can be used. The mixing ratio of water and the polar organic solvent can be arbitrarily set in consideration of the polymerization prescription of the adhesive polymer and the coating suitability of the adhesive composition.

  In addition, the organic solvent-based composition includes, as a solvent, the above-mentioned polar organic solvent or nonpolar organic solvent, for example, aliphatic hydrocarbons (for example, n-hexane, n-heptane, etc.), or aromatic hydrocarbons. (Eg, toluene, xylene, etc.) can be prepared alone or using mixtures thereof. The mixing ratio of each organic solvent can be arbitrarily set in consideration of the polymerized formulation of the adhesive polymer and the applicability of the adhesive composition.

  In the pressure-sensitive adhesive composition used in the present invention, the content of the solvent is not particularly limited, but is preferably based on 100 parts by weight of the pressure-sensitive adhesive polymer solid content contained in the pressure-sensitive adhesive composition used in the present invention. Is contained in an amount of 10 to 900 parts by weight, more preferably 40 to 500 parts by weight. If the content is less than 10 parts by weight, there may be a problem in the coating suitability of the pressure-sensitive adhesive composition, and if it exceeds 900 parts by weight, the drying property of the pressure-sensitive adhesive composition coating film may be poor.

The coating composition used for forming the color former-containing layer of the separation type adhesive label according to the present invention is not particularly limited as long as it contains a ninhydrin compound. What dissolved or disperse | distributed the ninhydrin compound in the various solvent used for the said adhesive composition, water, and / or an organic solvent can be used.
Furthermore, an acrylic resin, a polyester resin, a rubber resin, or the like can be added in order to improve the coating suitability and the adhesion with the transparent non-shrinkable base sheet. The content of the resin in the coating composition is not particularly limited, and may be appropriately selected in consideration of coating suitability and adhesion with a transparent non-shrinkable base sheet.

  The transparent non-shrinkable base material sheet used for the pressure-sensitive adhesive label type sheet (or pressure-sensitive adhesive label) according to the present invention is particularly limited as long as it is a transparent sheet capable of forming a layer of the pressure-sensitive adhesive composition on at least one surface thereof. It can be, for example, paper, natural or synthetic fiber material (eg woven or knitted fabric or non-woven fabric) film or sheet, or synthetic resin film or sheet. Examples of paper include glassine paper and tracing paper with high beating rate. Synthetic resins include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyester, polyvinyl acetate, polybutene, polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, Examples include various resins such as polyacrylonitrile, polycarbonate, polyamide, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, polyvinyl acetal, ethyl cellulose, cellulose triacetate, and hydroxypropyl cellulose. Moreover, these paper, a film, or a sheet | seat is used individually or as these laminated bodies.

  The pressure-sensitive adhesive label type sheet according to the present invention can be applied to any outer surface (outer surface) of the bottle, that is, the outer side surface, bottom surface, or upper surface of the bottle, and in particular, applied to the entire outer side surface and bottom surface. It is preferable to make it. Since the pressure-sensitive adhesive label-type sheet according to the present invention is mainly used by being attached to the outer surface (outer surface) of a curved bottle, it is preferable that the transparent non-shrinkable base sheet has flexibility. Furthermore, a bottle breakage preventing function can be imparted using a transparent non-shrinkable base sheet having cushioning properties. Further, a corona treatment or an ozone treatment is performed on the surface of the transparent non-shrinkable substrate sheet on which the color former-containing pressure-sensitive adhesive layer is formed or on the surface of the transparent non-shrinkable substrate sheet on which the color former-containing layer is formed, or Adhesion between the transparent non-shrinkable base sheet and the color former-containing pressure-sensitive adhesive layer or the color former-containing layer can be enhanced by providing an easy adhesion layer.

  The mixed pressure-sensitive adhesive label according to the present invention is prepared by subjecting the pressure-sensitive adhesive composition containing the ninhydrin compound represented by the general formula (I) to any known method (for example, knife coater, gravure coater, die coater, roll coater). , A coating method using a reverse coater, a screen coater, or the like) is applied on one surface of a transparent non-shrinkable base sheet, and a pressure-sensitive adhesive layer is provided. A release material is stuck on the color former-mixed pressure-sensitive adhesive layer of the mixed-type pressure-sensitive adhesive label obtained in this way, so that the color former-mixed pressure-sensitive adhesive layer before use can be protected. In addition, a color-forming agent-containing pressure-sensitive adhesive layer can be provided on the release-treated surface of the release material by the above-mentioned known method, and bonded to a transparent non-shrinkable base sheet to obtain the mixed-type pressure-sensitive adhesive label of the present invention.

  The separation-type adhesive label according to the present invention is obtained by applying the coating composition containing the ninhydrin compound represented by the general formula (I) to one surface of a transparent non-shrinkable base sheet by the known method. After forming the color former-containing layer, the pressure-sensitive adhesive composition that does not contain the color former is further coated on the color former-containing layer by the above-mentioned known method to provide a pressure-sensitive adhesive layer that does not contain the color former. Can be manufactured. It is possible to protect the pressure-sensitive adhesive layer before use by sticking a release material on the pressure-sensitive adhesive layer of the separated pressure-sensitive adhesive label obtained in this way. Further, a color former-containing layer is formed on one surface of the transparent non-shrinkable base sheet, and on the other hand, a pressure-sensitive adhesive layer not containing a color former is formed on the release-treated surface of the release material by the known method. By attaching the color former-containing layer and the pressure-sensitive adhesive layer, a separation-type pressure-sensitive adhesive label according to the present invention can be obtained.

  As the release material, a conventionally known pressure-sensitive adhesive sheet or that used for pressure-sensitive adhesive labels can be used as it is. For example, a release agent such as silicone, alkyd, or fluorine is applied to polylamination paper (paper laminated with polymer or resin), glassine paper, coated paper, polyester film, or polypropylene film as the base material of the release material A thing is preferably used, and a foam can also be used as a base material of a release material.

  The thickness of each layer of the pressure-sensitive adhesive label sheet (or pressure-sensitive adhesive label) according to the present invention is not particularly limited, but in the case of a mixed-type pressure-sensitive adhesive label, the transparent non-shrinkable base sheet is usually about 5 to 500 μm. The color former mixed pressure-sensitive adhesive layer is about 5 to 200 μm. In the case of a separation-type pressure-sensitive adhesive label, the transparent non-shrinkable base sheet is usually about 5 to 500 μm, the color former-containing layer is about 0.1 to 200 μm, and the pressure-sensitive adhesive layer is about 5 to 200 μm. All of the release materials are preferably about 5 to 300 μm.

  The color former-mixed pressure-sensitive adhesive layer of the mixed-type pressure-sensitive adhesive label according to the present invention may further contain a colorant. Similarly, the color former-containing layer and / or the pressure-sensitive adhesive layer of the separation-type pressure-sensitive adhesive label according to the present invention can further contain a colorant. By including a colorant in these layers, the result of the ninhydrin coloring reaction can be observed more clearly. In particular, when the bottle to which the pressure-sensitive adhesive label sheet (or pressure-sensitive adhesive label) according to the present invention is attached is transparent and the liquid filled in the bottle is transparent, it is preferable to use a colorant.

  In the present invention, for example, a light colorant (particularly, a white or yellow pigment or dye) is preferably used as the colorant. In this case, since the background can be lightened (particularly white), the distinction of the contrast between the leaking part and the non-leakage part can be improved, so that a high whiteness is more suitable. Further, when a fine powder (particularly white fine powder) is used as the colorant, it is effective for forming a smooth coating film. It is to be noted that, when the color former-containing pressure-sensitive adhesive layer containing fine powder (particularly white fine powder), the color former-containing layer and / or the pressure-sensitive adhesive layer is dried, generation of cracks due to drying shrinkage of those coating films is prevented. For this reason, in some cases, it may be preferable to partially use plate-like particles and fibrous particles together.

  As the colorant, either an inorganic substance or an organic substance can be used, and an inorganic substance is preferable in terms of quality stability. Specific examples include fine white powders such as silicic acid and silicates, magnesium hydroxide, magnesium carbonate, titanium oxide, magnesium oxide, calcium oxide, talc, acid clay, mica, kaolin, bentonite, or sericite. These white fine powders may be mixed and used. The particle size of these white fine powders is not particularly limited, but is preferably 10 μm or less. If the particle size of the white fine powder exceeds 10 μm, irregularities are likely to occur on the surface of the coating film, which may cause poor appearance and further decrease in physical properties of the adhesive. The blending amount of the white fine powder is preferably in the range of 5 to 70% by weight, more preferably 10 to 70% by weight in the color former-containing pressure-sensitive adhesive layer, the color former-containing layer, or the pressure-sensitive adhesive layer. . If it is less than 5% by weight, the whiteness becomes low, and there may be a problem in the detectability of the leaked portion. On the other hand, if it exceeds 70% by weight, the content ratio of the other components becomes low, so that the pressure-sensitive adhesive strength of the color former-containing pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer is reduced, or the coating suitability of the color former-containing layer is deteriorated. Sometimes.

  The color former-containing pressure-sensitive adhesive layer of the mixed pressure-sensitive adhesive label according to the present invention, or the color former-containing layer and / or the pressure-sensitive adhesive layer of the separation-type pressure-sensitive adhesive label according to the present invention, respectively, A reducing agent or antioxidant can be contained. These reducing agents or antioxidants have a function of suppressing the oxidative degradation of intermediates in a series of ninhydrin reaction steps and promoting the generation of a colored substance. However, it is not preferable to use a compound that inhibits the ninhydrin reaction or may itself cause a ninhydrin reaction.

  Examples of the reducing agent or antioxidant include L-ascorbic acid, L-ascorbyl stearate, L-ascorbyl palmitate, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), 2,2 ′. -Methylene-bis- (4-methyl-6-tert-butylphenol) or 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl An acrylate etc. can be used. In addition, a known reducing agent or antioxidant of phenol type, organic sulfur type, or phosphite type can be used.

  As described above, the heat-shrinkable sheet according to the present invention carries a color former-containing layer on one surface of a transparent heat-shrinkable substrate sheet. Also in the heat-shrinkable sheet of the present invention, the color former-containing layer may have a single layer structure or a structure of two or more layers. The heat-shrinkable sheet of the present invention in which the color former-containing layer has a single-layer structure is hereinafter referred to as a single-layer heat-shrinkable sheet, and the heat-shrinkable sheet of the present invention in which the color former-containing layer has a structure of two or more layers. Hereinafter, the adhesive sheet may be referred to as a multilayer heat shrinkable sheet.

  The single-layer heat-shrinkable sheet according to the present invention has a color former-containing layer having a single-layer structure on one surface of a transparent heat-shrinkable base sheet, and the general formula is contained in the single-layer color former-containing layer. A ninhydrin compound represented by (I) is contained as a color former. The multilayer heat-shrinkable sheet according to the present invention has a color former-containing layer and an auxiliary layer not containing one or more color formers on one surface of the transparent heat-shrinkable base sheet, The color former-containing layer contains the ninhydrin compound represented by the general formula (I) as a color former. The order of laminating the color former-containing layer and the auxiliary layer on the surface of the transparent heat-shrinkable substrate sheet is not particularly limited, but an auxiliary layer is provided on the surface of the transparent heat-shrinkable substrate sheet by contacting it. It is preferable to laminate a color former-containing layer.

  The content of the ninhydrin compound in the single-layer color former-containing layer or the color former-containing layer is not particularly limited, but the coating composition 100 used for forming the single-layer color former-containing layer or the color former-containing layer is not limited. It is contained in the part by weight, preferably in an amount of 0.5 to 50 parts by weight, more preferably 1.0 to 30 parts by weight. When the content is less than 0.5 parts by weight, the color of the leaked liquid content may become thin, and when it exceeds 50 parts by weight, the ninhydrin compound is uniformly dissolved in the coating composition. May become difficult and may impair application suitability. In the range of 2.5 parts by weight to 20 parts by weight, a clear color is obtained, which is particularly preferable.

  Formation of coating composition used for formation of single layer color former-containing layer of single-layer type heat-shrinkable sheet of the present invention, and color former-containing layer of multilayer type heat-shrinkable sheet, and formation of auxiliary layer of multilayer-type heat-shrinkable sheet All of the coating compositions (hereinafter collectively referred to as coating compositions) used in the above are substantially free of nitrogen-containing compounds. Here, “substantially free” means within the coating composition of the single layer color former-containing layer of the single-layer type heat-shrinkable sheet or within the coating composition of the color former-containing layer of the multilayer type heat-shrinkable sheet. This means that the nitrogen-containing compound is not contained in an amount that is greater than the amount that causes a ninhydrin reaction with the ninhydrin compound represented by the general formula (I) to cause coloration. In addition, in the auxiliary layer of the multilayer heat-shrinkable sheet, the amount is more than the amount that causes a ninhydrin reaction with the ninhydrin compound represented by the general formula (I) contained in the adjacent color former-containing layer to cause coloration. Means no nitrogen-containing compound.

  Examples of the nitrogen-containing compound that may cause a ninhydrin reaction to cause coloration when incorporated in the coating composition used in the present invention include the compounds described with respect to the pressure-sensitive adhesive composition. Such a nitrogen-containing compound cannot be contained in the coating composition used in the present invention.

The coating composition used in the present invention comprises at least the ninhydrin compound represented by the general formula (I) and various solvents (water and / or organic solvent) used in the pressure-sensitive adhesive composition for dissolving or dispersing them. . Further, if necessary, in consideration of coating suitability and / or adhesion to a transparent heat-shrinkable base sheet, a polymer or resin that is non-reactive (ninhydrin reaction negative) with the ninhydrin compound represented by the general formula (I). The binder consisting of can be added as appropriate.
As the binder, a polyester resin, an acrylic resin, a cellulose resin, a polyvinyl alcohol resin, or the like is preferably used.
Polyester resins include polyethylene terephthalate / polyethylene isophthalate copolymer or polylactic acid (racemic polymer), and acrylic resins include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate / methacrylic acid. n-butyl copolymer, n-butyl methacrylate / acrylic acid copolymer, etc., cellulose resins such as methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, cellulose acetate, etc., and polyvinyl alcohol resins as saponified Examples thereof include polyvinyl acetate, partially saponified polyvinyl acetate, an ethylene / vinyl alcohol copolymer, and polyvinyl butyral.

  The transparent heat-shrinkable base material sheet used for the heat-shrinkable sheet according to the present invention is particularly limited as long as it can form the color former-containing layer on at least one surface thereof, and is a transparent sheet having heat-shrinkability. For example, polyester films such as polyethylene terephthalate, polyethylene naphthalate, polylactic acid, poly (ε-caprolactone), polybutylene succinate, polyethylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer , Polyolefin films such as polypropylene, polystyrene, polyvinyl chloride, and polyvinylidene chloride, and uniaxially or biaxially stretched films thereof.

  The transparent heat-shrinkable base sheet used in the present invention can be produced by, for example, a casting method, an extrusion method, or a calendar method.

  The thickness of each layer of the heat-shrinkable sheet according to the present invention is not particularly limited, but in the case of a single-layer heat-shrinkable sheet, the transparent heat-shrinkable base sheet is usually about 5 to 500 μm. The monolayer color former-containing layer is about 0.1 to 200 μm. In the case of a multilayer heat-shrinkable sheet, the transparent heat-shrinkable base sheet is usually about 5 to 500 μm, the color former-containing layer is about 0.1 to 200 μm, and the total thickness of the auxiliary layers is about 0. .1 to 200 μm.

  The single-layer color former-containing layer of the single-layer heat-shrinkable sheet according to the present invention can further contain a colorant as in the case of the pressure-sensitive adhesive label-type sheet. Similarly, the color former-containing layer and / or the auxiliary layer of the multilayer heat-shrinkable sheet according to the present invention can further contain a colorant. By including a colorant in these layers, the result of the ninhydrin coloring reaction can be observed more clearly. In particular, when the bottle carrying the heat-shrinkable sheet according to the present invention is transparent and the liquid filled in the bottle is transparent, it is preferable to use a colorant. As the colorant, the colorant described for the pressure-sensitive adhesive label type sheet can be used.

  The heat-shrinkable sheet of the present invention can be produced by applying the coating composition to a transparent heat-shrinkable substrate sheet by a known method for applying the pressure-sensitive adhesive composition for the mixed pressure-sensitive adhesive label.

  The leakage detection sheet according to the present invention can be used by being carried in a container filled with a liquid containing any amino compound that causes a ninhydrin reaction by the ninhydrin compound represented by the general formula (I). In the case of an adhesive label type sheet, it can be used by being affixed to the outer surface of the container, and in the case of a heat shrinkable sheet, it is heat-shrinked on the outer surface of the container and used by being closely adhered and fixed to the container. Can do. Containers to which the leakage detection sheet according to the present invention is carried include any container made of a material that is susceptible to breakage or cracking when subjected to a physical impact, and typically generates cracks. Easy to use glass or earthenware bottles. The leakage detection sheet according to the present invention enables detection even when a minute crack is generated in the liquid-filled container and liquid content leakage that is normally impossible or difficult to visually confirm is generated. For this reason, it is preferable to use it supported on the entire outside of the container. In addition, since it is carried in a container as a sheet, it preferably has a function as a display body that correctly specifies the product name, usage, and dose, and in particular, in the case of an adhesive label type sheet, it has cushioning properties. Is preferred.

  The leak detection sheet according to the present invention can be used by being carried in a container filled with a liquid containing any amino compound that causes a ninhydrin reaction by the ninhydrin compound represented by the general formula (I). For example, when the leakage detection sheet of the present invention is a mixed-type pressure-sensitive adhesive label among pressure-sensitive adhesive label-type sheets, it can be used by being carried on a container in a state where a color former-mixed pressure-sensitive adhesive layer is adhered to the outer surface of the container. . Moreover, when it is a separation-type pressure-sensitive adhesive label among the pressure-sensitive adhesive label-type sheets, the pressure-sensitive adhesive layer can be carried on a container while being directly attached to the outer surface of the container.

  On the other hand, when the leakage detection sheet of the present invention is a single-layer heat-shrinkable sheet among heat-shrinkable sheets, the heat-shrink treatment is performed with the color-developer-containing layer having a single-layer structure in direct contact with the outer surface of the container. Can be carried out in close contact with the outer surface of the container. In the case of a multilayer heat-shrinkable sheet, the heat-shrinking treatment can be carried out in a state where the color former-containing layer is in direct contact with the outer surface of the container, and can be carried in close contact with the outer surface of the container. In addition, when using a heat-shrinkable sheet, it is preferable to use the container which consists of a material which does not deform | transform at the heat-shrink processing temperature of a heat-shrinkable sheet.

  The liquid filled in the container includes any liquid that is orally or parenterally consumed by animals including humans, and particularly when contaminated with pathogenic bacteria from a cracked portion of the container, It is suitable for use in liquids that may cause infection, such as liquid pharmaceuticals, liquid nutrients, liquid foods, or liquid seasonings. Examples of other liquids include reagents such as chemicals.

  Here, the “amino compound” includes any compound that causes a ninhydrin reaction by the ninhydrin compound represented by the general formula (I), and examples thereof include amino acids, oligopeptides, polypeptides, and proteins. . These amino compounds are not limited to compounds blended as active ingredients of the liquid filled in the container, but are compounds blended as additives, and compounds blended as indicators. You can also. For example, in the case of a liquid medicine filled in an ampoule bottle or a vial, it is an amino compound contained as an active ingredient or a carrier, or the liquid filled in the bottle is an original active ingredient or carrier. When an amino compound is not contained, the amino compound can be added as an indicator and used for leakage detection.

  The “liquid” to be filled in the container for carrying the leakage detection sheet according to the present invention is not limited to a liquid that is liquid throughout the filling period. That is, it includes those that are frozen during transportation and storage and are thawed immediately before use to become liquid. The liquid includes a solution, a dispersion, a suspension, or an emulsion.

  The container for carrying the leakage detection sheet according to the present invention and the liquid filled in the container may be transparent or colored, respectively. When both the container and the liquid are transparent, it is preferable to add a colorant to the coloring layer. That is, in the case of a mixed-type pressure-sensitive adhesive label, a colorant is added to the color former-mixed pressure-sensitive adhesive layer. In the case of a separation-type pressure-sensitive adhesive label, a colorant is added to the color former-containing layer and / or the pressure-sensitive adhesive layer. Is preferred. Further, in the case of a single-layer heat-shrinkable sheet, a colorant is added to the single-layer color-shrinking agent-containing layer, and in the case of a multilayer heat-shrinkable sheet, the color former-containing layer and / or the auxiliary layer. It is preferable to add a colorant.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.

<< Copolymer Preparation Example 1 >>
A hydrophilic acrylic ester copolymer solution was prepared from the following compounds.
2-methoxyethyl acrylate 95 parts by weight Acrylic acid 5.0 parts by weight 2,2′-azobisisobutyronitrile 0.15 parts by weight Ethyl acetate 200 parts by weight Toluene 30 parts by weight

  Specifically, in a 500 mL four-necked flask, 95 parts by weight of 2-methoxyethyl acrylate, 5.0 parts by weight of acrylic acid, 0.15 parts by weight of 2,2′-azobisisobutyronitrile, and ethyl acetate 200 parts by weight were mixed and polymerized at 60 ° C. for 12 hours in a nitrogen atmosphere. After cooling the product to 20 ° C., 30 parts by weight of toluene was added to prepare a hydrophilic acrylate copolymer solution. This hydrophilic acrylate copolymer solution contained a hydrophilic acrylate copolymer in an amount of about 30% by weight. The hydrophilic acrylate copolymer solution thus obtained was used as a main agent in Examples and Comparative Examples described later.

<< Copolymer Preparation Example 2 >>
A hydrophobic acrylic ester copolymer solution is obtained by repeating the operation described in the copolymer preparation example 1 except that 95 parts by weight of n-butyl acrylate is used instead of 95 parts by weight of 2-methoxyethyl acrylate. Was prepared. This hydrophobic acrylic ester copolymer solution contained the hydrophobic acrylic ester copolymer in an amount of about 30% by weight. The hydrophobic acrylic ester copolymer solution thus obtained was used as a main agent in Examples and Comparative Examples described later.

<< Adhesive Composition Preparation Example 1 >>
A pressure-sensitive adhesive composition was prepared from the following blending components.
Main agent: Hydrophilic acrylic acid ester copolymer solution 100 parts by weight Colorant: Ninhydrin 5.0 parts by weight Crosslinking agent: Metal chelate compound 1.5 parts by weight Diluent: Methyl ethyl ketone 10 parts by weight Colorant: Titanium oxide 10 parts by weight

  Specifically, 100 parts by weight of the hydrophilic acrylate copolymer-containing main agent prepared in the above-mentioned copolymer preparation example 1, 5.0 parts by weight of ninhydrin as a colorant, and a metal chelate compound as a crosslinking agent [M-5A; manufactured by Soken Chemical Co., Ltd.] 1.5 parts by weight, titanium oxide as a colorant [acrylic resin dispersion; Olivevine BXX2026; manufactured by Toyo Ink Manufacturing Co., Ltd.] 10 parts by weight, and a diluent solvent A pressure-sensitive adhesive composition was obtained by stirring and mixing 10 parts by weight of methyl ethyl ketone. Hereinafter, this pressure-sensitive adhesive composition is referred to as a hydrophilic pressure-sensitive adhesive composition A.

<< Adhesive Composition Preparation Example 2 >>
Instead of 100 parts by weight of the hydrophilic acrylate copolymer-containing main agent prepared in the copolymer preparation example 1 as the main agent, the hydrophobic acrylate copolymer solution 100 prepared in the copolymer preparation example 2 A pressure-sensitive adhesive composition was produced in the same manner as pressure-sensitive adhesive composition preparation example 1 except that parts by weight were used. Hereinafter, this pressure-sensitive adhesive composition is referred to as a hydrophobic pressure-sensitive adhesive composition B.

<< Adhesive Composition Preparation Example 3 >>
A pressure-sensitive adhesive composition was produced in the same manner as the pressure-sensitive adhesive composition preparation example 1 except that titanium oxide as a colorant was not used. Hereinafter, this pressure-sensitive adhesive composition is referred to as non-colored hydrophilic pressure-sensitive adhesive composition C.

<< Adhesive Composition Preparation Example 4 >>
A pressure-sensitive adhesive composition was produced in the same manner as pressure-sensitive adhesive composition preparation example 1 except that ninhydrin as a color former was not used. Hereinafter, this pressure-sensitive adhesive composition is referred to as a ninhydrin-free pressure-sensitive adhesive composition D.

<< Adhesive Composition Preparation Example 5 >>
A pressure-sensitive adhesive composition was produced in the same manner as pressure-sensitive adhesive composition preparation example 1 except that ninhydrin as a color former was not used and titanium oxide as a colorant was not used. Hereinafter, this pressure-sensitive adhesive composition is referred to as a ninhydrin-free non-colored pressure-sensitive adhesive composition E.

<< Coating composition preparation example 1 >>
A polyester resin solution was prepared by dissolving 30 parts by weight of a polyester resin [Byron 20SS; manufactured by Toyobo Co., Ltd .; solid content 30% by weight] in 56 parts by weight of toluene and 14 parts by weight of methyl ethyl ketone. To 100 parts by weight of the polyester resin solution thus obtained, 1.5 parts by weight of ninhydrin, 12.5 parts by weight of methyl ethyl ketone, and titanium oxide as a colorant [acrylic resin dispersion; olivine BXX2026; Toyo Ink Manufacturing Co., Ltd. Manufactured] 10 parts by weight was added and dissolved to prepare ninhydrin-containing coating composition A.

<< Coating composition preparation example 2 >>
A ninhydrin-free coating composition B was prepared in the same manner as in the coating composition preparation example 1 except that ninhydrin was not used.

Example 1
As the pressure-sensitive adhesive composition, a hydrophilic pressure-sensitive adhesive composition A was used. A polyethylene terephthalate film (manufactured by Lintec Co., Ltd., SP-PET3811, thickness = 38 μm) that has been treated with a silicone resin on one side is prepared as a release material, and a corona treatment is applied to one side as a base sheet. A polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror T60, thickness = 25 μm) was prepared. The said hydrophilic adhesive composition A was apply | coated to the peeling process side surface of the said peeling material so that the thickness after drying might be 35 micrometers, and it dried at 100 degreeC for 2 minutes. Subsequently, the corona-treated side surface of the substrate sheet was bonded to the pressure-sensitive adhesive composition to produce a mixed-type pressure-sensitive adhesive label A according to the present invention.

Example 2
A mixed pressure-sensitive adhesive label B according to the present invention was produced in the same manner as in Example 1 except that the hydrophobic pressure-sensitive adhesive composition B was used in place of the hydrophilic pressure-sensitive adhesive composition A as the pressure-sensitive adhesive composition. .

Example 3
The mixed pressure-sensitive adhesive label C according to the present invention was used in the same manner as in Example 1 except that the non-colored hydrophilic pressure-sensitive adhesive composition C was used in place of the hydrophilic pressure-sensitive adhesive composition A as the pressure-sensitive adhesive composition. Manufactured.

<< Comparative Example 1 >>
A comparative pressure-sensitive adhesive label D was produced in the same manner as in Example 1 except that the ninhydrin-free pressure-sensitive adhesive composition D was used in place of the hydrophilic pressure-sensitive adhesive composition A as the pressure-sensitive adhesive composition.

Example 4
On the corona-treated surface of a polyethylene terephthalate film [Lumirror T60, thickness = 25 μm, manufactured by Toray Industries, Inc.] having a corona treatment on one side, the thickness after drying the ninhydrin-containing coating composition A is 2.5 μm. And dried at 70 ° C. for 2 minutes.
On the other hand, the thickness after drying the ninhydrin-free pressure-sensitive adhesive composition D on the release-treated surface of a polyethylene terephthalate film [manufactured by Lintec Corporation, SP-PET 3811, thickness = 38 μm] peel-treated with a silicone resin on one side. Was applied to a thickness of 35 μm and dried at 100 ° C. for 2 minutes. Subsequently, the coating composition side of the polyethylene terephthalate film coated with the coating composition A and the ninhydrin-free pressure-sensitive adhesive composition D were bonded together to produce a separation-type pressure-sensitive adhesive label E according to the present invention.

Example 5
As the pressure-sensitive adhesive composition, the separation-type pressure-sensitive adhesive label of the present invention was used in the same manner as in Example 4 except that the ninhydrin-free non-colored pressure-sensitive adhesive composition E was used instead of the ninhydrin-free pressure-sensitive adhesive composition D. F was produced.

<< Comparative Example 2 >>
A comparative pressure-sensitive adhesive label G for comparison was produced in the same manner as in Example 4 except that instead of ninhydrin-containing coating composition A, ninhydrin-free coating composition B was used as the coating composition.

Example 6
The thickness after drying the ninhydrin-containing coating composition A on the corona-treated surface of a heat-shrinkable polyester film [Toyobo Co., Ltd., Toyobo Space Clean S7553, thickness = 50 μm] having a corona treatment on one side. It was applied to a thickness of 5 μm and dried at 60 ° C. for 30 seconds and then at 50 ° C. for 1 minute to prepare a heat-shrinkable sheet H having a ninhydrin-containing coat layer.

<< Comparative Example 3 >>
A comparative heat-shrinkable sheet I was prepared in the same manner as in Example 6 except that instead of the coating composition A, the coating composition B containing no ninhydrin was used as the coating composition.

[Evaluation of the physical properties]
(1) Evaluation method A color test was conducted on the leakage detection sheets prepared in the examples and comparative examples. In the case of the pressure-sensitive adhesive label, it was carried out after removing the adhesive label release material and exposing the coated and dried pressure-sensitive adhesive surface. A saline solution (saline concentration of 9.0 g / L) in which 1.0% by weight of glycine (amino acid) is dissolved is added to each of the color development layers of each leakage detection sheet by 10 drops (about 10 mg) at 10 locations. The solution was dropped and allowed to stand for 2 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Sheets for leakage detection (Examples 1, 2, 4, and 6 and Comparative Examples 1 and 2) containing a colorant are bonded to a transparent glass, the color state is observed from the label surface, and no colorant is contained. Leakage detection sheets (Examples 3 and 5 and Comparative Example 3) were bonded to white fine paper, and the colored state was observed from the surface of the leakage detection sheet.
A similar test using a suspension containing 0.39% by weight of insulin (oligopeptide) instead of glycine physiological saline and leaving it in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 5 hours, and human serum albumin (Protein) A similar test in which 25% by weight of physiological saline (saline concentration: 9.0 g / L) was allowed to stand in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 8 hours was also performed. The color state was observed.
The observation results were evaluated in the following three stages.
A: A blue-violet coloration with good visibility was confirmed.
B: Pale purple coloration was confirmed.
C: No coloration is observed at all.

(2) Results The results are shown in Table 1 below.

  The leakage detection sheet according to the present invention can detect leakage easily by visual inspection even when liquid content leakage, which is usually impossible or difficult to visually confirm, can be detected. It can be effectively used to detect the occurrence of cracks in filled ampoule bottles and vials. Liquid investigational drugs contain a large amount of physiological saline, but they contain amino acids such as glycine, and recent proteome technology (analysis technology for all proteins produced by specific cells and tissues) and gene analysis technology The leakage detection sheet according to the present invention is effective even when considering that many useful protein preparations and peptide preparations are developed with the progress of the above.

It is typical sectional drawing which shows the state which affixed the mixing type adhesive label by this invention on the surface of the bottle. It is typical sectional drawing which shows the state which stuck the separation-type adhesive label by this invention on the surface of the bottle.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Transparent base material sheet 2 ... Color former mixed adhesive layer 3 ... Color former containing layer 4 ... Color former-free adhesive layer 5 ... Bottle 10 ... Mixed adhesive label 10A: Separable adhesive label

Claims (15)

A sheet provided on the outer surface of a container for filling an amino compound-containing liquid, for detecting leakage of the amino compound-containing liquid due to breakage of the container, on one surface of the transparent substrate sheet, as a color former Formula (I):

(Wherein R is a hydrogen atom or an alkyl group)
The leakage detection sheet according to claim 1, comprising a color-developing layer that contains a ninhydrin compound represented by formula (1) and substantially does not contain a nitrogen-containing compound.   The leakage detection sheet according to claim 1, wherein the transparent base sheet is a transparent non-shrinkable base sheet or a transparent heat-shrinkable base sheet.   The leakage detection sheet according to claim 1, wherein the transparent substrate sheet is a transparent non-shrinkable substrate sheet, and the color-forming layer is a color-forming pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition.   The leakage detection sheet according to claim 3, wherein the color-forming pressure-sensitive adhesive layer has a single-layer structure of a color-forming agent-mixed pressure-sensitive adhesive layer containing the ninhydrin compound in a pressure-sensitive adhesive composition.   The leakage detection sheet according to claim 4, wherein the color former-mixed pressure-sensitive adhesive layer contains a colorant.   The color-forming pressure-sensitive adhesive layer is provided on one surface of the transparent base sheet, and is provided on the color-forming agent-containing layer that does not contain a pressure-sensitive adhesive composition and contains the ninhydrin compound, and the color-forming agent-containing layer. The leakage detection sheet according to claim 3, comprising a two-layer structure with an adhesive layer.   The leakage detection sheet according to claim 6, wherein the color former-containing layer and / or the pressure-sensitive adhesive layer further contains a colorant.   The leakage detection sheet according to claim 1, wherein the transparent base sheet is a transparent heat-shrinkable base sheet, and the color developing layer is a color former-containing layer that does not contain an adhesive composition.   The leakage detection sheet according to claim 8, wherein the color former-containing layer is a single-layer color former-containing layer having a single-layer structure containing the ninhydrin compound.   The leakage detection sheet according to claim 9, wherein the single layer color former-containing layer further contains a colorant.   The leakage detection sheet according to claim 8, wherein the color former-containing layer is a color former-containing layer having a multilayer structure of the single-layer color former-containing layer and one or more auxiliary layers not containing the color former. .   The leakage detection sheet according to claim 11, wherein the monolayer color former-containing layer and / or the auxiliary layer further contains a colorant.   A container for carrying the leakage detection sheet according to any one of claims 1 to 12 on an outer surface in a state in which the coloring layer is in contact with the outer surface of the container.   A container for carrying the leakage detection sheet according to any one of claims 3 to 7 on the outer surface in a state where the coloring adhesive layer is in contact with the outer surface of the container.   The container which carries on the outer surface in the state which heat-shrinked the said sheet | seat for leak detection as described in any one of Claims 8-12, and contacted the color former containing layer with the outer surface of the container.

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